Moistureproof sheet wrapping material



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' James A. Mitchell, Kenmore, N. Y., asalgnor to E. I. du Pont de Nemonrs a Company, Wllmingtom Del., a corporation of Delaware lilo Drawing.

10 Claims.

This invention relates to moistureproof sheet wrapping material, and more particularly to the moisture-proofing of regenerated cellulose and like film. It especially appertains to. the anchor-. ing. of moistureproof coatings to the base sheet.

Recently there has appeared in commerce a transparent'moistureproof sheet wrapping material consisting of a base sheet of regenerated cellulose film coated with a moistureprooilng coating composition. The manufacture of such a base sheet is described in U. S. A. Patent No. 1,548,864 (Brandenbergez'). and the coating 'of the like with a moistureprooflng composition is .described in U. S. A. Patent No. 1,737,187 (Charch 8a Prindle). When products containing considerable water (cheese, fish, fresh vegetables, etc.) are wrapped in suchmaterial, the surface coating loosens in a few hours. As a result, the effectiveness of the wrapping is very appreciably reduced. Amongthe various plans which have been proposed for avoiding or overcoming this failing is that of anchoring the moisture-proof Application November 1, 1939, Serial No. 302,318

coatingtothe base sheet by means .of an intermediate coat. Details of such procedures are disclosed in U. S. A. Patent 1,962,338 (Charch).

The primary objects of this invention were to improve transparent sheet wrapping materials having anchored moistureproof coatings and the processes of their production. Another object was the production of a flexible, odorless, colorless, transparent, moisture-proof sheet wrapping material comprising a regenerated cellulose film having a moistureprooflng coating which would adhere tenaciously thereto even in the presence of water. Further objects were to devise a simple process applicable to existing and conventional equipment for anchoring moistureproofing coatings to regenerated cellulose and like film, to devise an efllcient and economical process applicable to high speed coating equipment for anchoring moistureproofing coatings to regenerated cellulose, to improve the. anchorage of moistureproof coatings comprising a film former, a moistureprooflng agent, a blending agent and a plasticizer to regenerated cellulosic film, to produce a moistureproofed regenerated cellulose him having a harder and more wear-resistant coating than heretofore obtainable with the coating compositions containing anchoring media having drying characteristics, to produce a moistureproofed regenerated cellulose film having a completely odorless anchoring medium with drying characteristics, and to anchor a moistureprooflng coating to a regenerated eral advance in the art, and other objects which I will appear hereinafter, are also contemplated.

Surprisingly, it has now been found that an intermediate coating of a 'butadiene polymer having drying characteristics will securely adhere a-moistureprooflng coating to regenerated cellulose film, and that the resulting moistureproof sheet wrapping material is greatly superior to the products heretofore known.

In general, coatings of such material are produced by dispersing the dloleflnic hydrocarbon polymer together with modifying agents if they are desired) in a suitable organic liquid solvent, applying the same to a regenerated cellulose web, heating to a suitable temperature in air or oxygen (preferably at about 100 C.)'. until the polymer is "cured and the coating relatively non-tacky, and thereafter top coating with a moistureprooflng lacquer of any desired type. The use of a drying catalyst in the intermediate coating composition is preferred.

From the following description and specific examples, in which are disclosed certain embodiments. of the invention as well as details as what is believed to be the best mode for carrying out the invention, it will be aparent how the foregoing objects and related ends are accomplished. The parts are given by weight throughout the application.

Example I A web of regenerated cellulose was coated with a solution consisting of:

The solvent was evaporated at about 100 C., and the coated sheet maintained at this temperature until cured," that is, until the coating had be- ,come relatively non-tacky. This required apcellulose film with a butadiene polymer. A genproximately 10 minutes. The resulting web was then top coated with a moistureproofing lacquer having the composition:

Parts Nitrocellulose (11.6% N) Paraflin wax (M. P. 60 C.) 3 Ester gum 7 Dicyclohexyl phthalate 20 Dibutyl phthalate 1o Ethyl acetate 450 Ethyl al 35 Toluene 245 After application of the surface coating composition the resulting material was subjected to a temperature approximating (or slightly higher than) the melting point of the wax (for specific detailslsee U. S. A. Patent 1,826,699 to Charch & Prindle). The resulting sheet material had a permeability value of 20, and the moistureproofing coating was still anchored to the base sheet of regenerated cellulose after being immersed in water at 25 for 166 hours.

Example If A web of regenerated cellulose was coated with a solution consisting of:

. Parts Butadiene polymer 3 Polymerized styrene 2 Cobalt naphthenate (as Co) g 0.005 Toluene 95 The solvent was evaporated at about 100 C., and the coated sheet maintained at this temperature until "cured. This required approximately 10 minutes. The resulting web was then top coated with a moistureproofing lacquer having the composition: 1

Parts Nitrocellulose. (11.6% N) 60 Paraflln wax (M. P. 60 C.) 3 Ester gum 7 Dicyclohexyl phthalate 20 Dibutyl phthalate 10 Ethyl acetate 450 Ethyl alcohol 35 Toluene 245 Example III A web of regenerated cellulose was coated with a solution consisting of Parts Butadiene polymer 9 Paraffin wax (M. P. 60 C.) 1 Cobalt naphthenate (as Co) 0.03 Toluene 90 The solvent was evaporated at about 100 C.,' and the coated sheet maintained at this temperature until gcuredf This required approximately 10 minutes. The resulting web was then top coated with a moistureproofing lacquer having the composition:

Parts Nitrocellulose (11.6% N) 60 Parafiin wax (M. P. 60 C.) 3 Ester gum '7 Dicyclohexyl phthalate 20 'Dlbutyl phthalate 10 Ethyl acetate 450 Ethyl alcohol. 35 Toluene 245 After application of the surface coating composition the resulting material was subjected to a temperature approximating (or slightly higher than) the melting point of the wax. The resulting sheet material had a permeability value 01' 20, and the moistureproofing coating was still anchored to the base sheet of regenerated cellulose after being immersed in water at C. for 120 hours.

Example IV A web of regenerated cellulose was coated with a solution consisting of:

Parts Butadiene polymer 9 Paraflin wax (M. P. 60 C.) 1 Cobalt naphthenate (as Co) 0.005 Manganese naphtenate (as Mn) 0.005 Toluene 90 The solvent was evaporated at about 100 C., and

the coated sheet maintained'at this temperature until "cured, that is, until the coating had become relatively non-tacky. This required approximately 6 minutes. The resulting web was then top coated with a moistureproofing lacquer having the composition:

Parts Ethyl cellulose (45%-48% ethoxy) 55 Parafiln wax (M. P. 60 C.) 5 Ester gum 25 Dicyclohexyl phthalate 15 Toluene"; 580 Ethyl alcohol 150 After application of the surface coating composition the resulting material was subjected to a temperature approximating (or slightly higher than) the melting point of the wax. The resulting sheet material had a permeability value of 2, and the moistureproofing coating was still anchored to the base sheet of regenerated cellulose after being immersed in water at 25 C. for 72-hours.

Example V A web of regenerated cellulose was coated with a solution consisting of Parts Butadiene polymer 9 Paraifin wax (M. P. 60 C.) 1 Cobalt naphthenate (as Co) 0.005 Manganese naphthenate (as Mn) 0.005 Toluene The solvent was evaporated at about 100 C., and

the coated sheet maintained at this temperature until cured, that is. until the coating had become relatively non-tacky. This required approximately 6 minutes. then top coated with a moistureproofing lacquer having the composition:

Parts Butyl methacrylate polymer Paraflin wax (M. P. 60 C.) 5 Toluene 730 After application of the surface coating composition the resulting material was subjected to a temperature approximating (or slightly higher than) the melting point of the wax. The resulting sheet material had a permeability value of 260, and the moistureproofing coating was still anchored to the base sheet of regenerated cellulose after being immersed in water at 25 C. for 72 hours.

The resulting web was proximately 6 minutes.

Example VI A web of regenerated cellulose was coated with a solution consisting of:

Parts Butadiene polymer 9 Paraflln wax (M. P. 60 C.) 1 Cobalt naphthenate (as 0.005 Manganese naphthenate (as Mn) 0.005 Toluene L 90 The solvent was evaporated at about 100 C... and

the coated sheet maintained at this temperature until cured," that is, until the coating'had become relatively non-tacky. This required approximately 6 minutes. The resulting web was then top coated with a moistureprooflng lacquer having the. composition:

Parts Pliolite 90 Paranin wax (M. P. 60 C.) Tolue 730 'Pliolite is a thermoplastic rubber derivative made by condensing rubber with a catalyst such as tin tetrachloride (see Pager Trade Journal page 96, February 23. 1939, J. I. E. XXVI, 125 and-U. S. A. Patents Nos. 1,797,188, 1,846,247, 1,853,334 and 2 52,391). The chemical ture is also described in ubber Age, April 1939, and J. I. E. C. XIX. 1033.

Example VI! A web of regenerated cellulose was coated with.

a solution consisting of:

l I Parts Butadiene polymer 9 Paraflln wax (M. P. 60 C.) 1

Cobalt naphthenate (as Co) 0.005 Manganese naphthenate (as Mn) 0.005 Toluene 90 The solvent was evaporated at about, 100 C., and

struc- I Example VIII Aweof regenerated cellulose was coatedwlith a solution consisting of:

Parts Butadiene polymer 9 Paramn wax (M. P. 60 C.) 1 Manganese naphthenate (as Mn) 0.01 Toluene 90 V The solvent was evaporated and the coated sheet "cured" at about 100 C. This required approxithe coated sheet maintained at this temperature until cured, that is, until the coating had becom relatively non-tacky. This required ap- The resulting web was then top coated with 9, moistureproofing lacquer having the composition:

9 Parts Chlorinated rubber (65%-68% Cl) l Paraflin wax (M. P. 60 C.) 6 Damarresin I 10 .Dicyclohexyl phthalate 12 Dibutyl phthalate l2 Tolue 730 After applicationoi the surface coating compositionthe resulting material was subjected to 48 hours.

9, temperature approximating (or slightly higher Toluene a solution consisting of mately 5 minutes. The resulting web having only this single coat had a permeability value of 2, and the coating was still anchored to the base sheet after 96 hours immersionin water at 25 C.

Example IX A web of regenerated cellulose was coated with a solution consisting of:

. Parts Butadiene polymer 9 Paraflin wax (M. P. 60 C.) 1

Cobalt Oilsolate (as Co) 0.01

Cobalt Oilsolate'is a s nthetic oil-soluble drier. Its prcfiaration is described the atents cited in the J. E. C. XXVI 1268-71 article a out its structure and properties.

The solvent was evaporated at about 100 C., and the coated sheet maintained at this temperature untilcured, that is, until the coating had become relatively non-tacky. This required approximately 7 minutes. The resulting-web having only this single coat had a permeability value 01' 5, and the coating was still anchored to the base sheet of regenerated cellulose. after being immersed in water at 25 C. for 144 hours.

Example X A web of regenerated cellulose was coated with Parts Butadiene polymer 40 Paraffin wax (M. P. 60 C.) 3 Ethyl cellulose (45%-48% ethoxy) 32 Ester g m 15 Dicyclohexyl phthalate 10 Cobalt naphthenate (as CO).\.----, 0.04 Toluene 5 80 Ethyl alcohol The solvent was evaporated at about 100 C., and the coated sheet maintained at this temperature until "cured," that is, until the coating had become relatively non-tacky. This required approximately 3 minutes. The resulting web having only this single coat had a permeability value of 100, and the coating was still anchored to the base sheet of regenerated cellulose after being immersed in water at 25 C. for 23 hours.

'When the same base sheet was coated under the same conditions with a similar composition, replacing the butadiene polymer with the ethyl cellulose, that is, a composition having 72 parts ethyl cellulose and the same amounts of paraflln wax, ester gum, dicyclohexyl phthalate, toluene and ethyl alcohol, a sheet was obtained which had a permeability value of 10, and which had its coating loosened by two hours immersion in water under the afore-mentioned conditions.

a solution consisting of:

\in. Parts Butadiene polymer 30 Paraflln wax (M. P. 60C.) 3 Nitrocellulose (11.6% N)--. 30 Ester g 7 Dicyclohexyl phthalate Dibutyl phthaiate 10 Manganese naphthenate (as Mn) 0.08 Toluene 245 Ethyl acetate 450 Ethyl alcohol----,. 35

The solvent was evaporated at about 100 C., and the coated sheet maintained at this temperature until cured," that is, until the coating hadbecome relatively non-tacky. This required approximately 8 minutes. The resulting web having only this single coat had a permeability value of 25, and the coating was still anchored to the base sheet of regenerated cellulose after being immersed in water at C. for 24 hours.

When the same base sheet was coated under the same conditions with a similar composition, replacing the butadiene polymer with nitrocellulose, that is, a composition having 60 parts nitrocellulose and the same amounts of parafiin,

ester ,gum, dicyclohexyl phthalate, dibutyl phthalate, toluene, ethyl'acetate and ethyl alcohol, a sheet was obtained which had a permeability value of 20,-and which had its coating loosened by 6 hours immersion in water under the aforementioned conditions.

Example XII A web of regenerated cellulose was coated with a solution consisting of:

Parts The solvent was evaporated at about 100 C., and the coated sheet maintained at this temperature until cured," thatis, until the coating had become relatively non-tacky. Thisrequired approximately 8 minutes. The resulting web having tained by heating the mixture consisting of:

The solvent was evaporated at about 100 C., and the coated sheet maintained at this temperature until cured, that is, until the cpating had become relatively non-tacky. This required approximately 8 minutes. The resulting web having only this single coat had a permeability value of 230, and the coating was still anchored to the base sheet of regenerated cellulose after being immersed in water at 25 C. for 24 hours.

When the same basesheet was coated under the same conditions with a similar composition, replacing the butadiene polymer with Pliolite resin, that is, a composition having 90 parts Pliolite resin and the same amounts of paraflin and toluene, a sheet was obtained which had apermeability value of .5, and which had its coating loosened by 4 hours immersion in water under the aforementioned conditions.

The viscous light yellow oily butadiene polymer utilized in the specific examples was ob- Parts Butadiene Benzene n-Butyraldehyde .Catalyst (equal parts of copper acetatef/HzO, copper metal, iron powder, ferrous oxide) 480 for 5 hours at 160 C. with stirring, cooling, diluting with 6650 parts of benzene, filtering oif the catalyst, treating the filtrate with carbon black, evaporating oil the benzene and by-prod- 'uct vinyl-cyclohexene. This product flowed slowly at room temperature (20 C.), and when diluted to a 58% solution in a high boiling aliphatic solvent (V. M. 8: P. naphtha-B. P. 95-195 C.) had a viscosity of -W in the Gardner- Holdt scale at 70 F. Its iodine number was slightly greater than 400 (e. 8. 407-415).

In general the polymeric substances employed as. anchoring media in this invention can be obtained' by polymerizing conjugated 'dioleflnic only this single coat had a permeability value of 80, and the coating was still anchored to the base sheet of regenerated cellulose after being immersed in water at 25 C. for 48 hours.

When the same base sheet was coated under the same conditions with a similar composition, replacing the butadiene polymer with butyl methaerylate polymer, that is, a composition having 94 parts of butyl methacrylate polymer and the same amounts of paraflin wax, cobalt naphthenate and toluene, a sheet was obtained which had a' permeability value of 20 and which had its coating loosened by four hours immersion in water under the aforementioned conditions.

Example XIII A web of regenerated cellulosewas coated with a solution consisting of:

- Parts Butadiene polymer Paraflin wax (M. P. 60 C.) 10

' Pliolite resin 45 Cobalt naphthenate (as Co) 0.03 Manganese naphthenate (as Mn) 0.03 Toluene 730 copper with weak acids in hydrocarbons such as butadiene or its various ".open chain homologs like isoprene, methyl butadiene and 2:3-di-methyl butadiene. The low condensed soluble polymer products from butadiene have been found to be especially well suited for the purposes of this invention.

Preferably the polymerization is eifeeted under pressure at elevated temperatures in the presence of catalysts such as sodium or salts of the presence of a carbonyl compound. The presence of an inert organic liquid (solvent) is desirable and is preferred. The details of the processes for the preparation of the bodies are extensive and in' the interest of brevity are omitted from this specification. In general any of the products disclosed in and/or produced according to U. S. A. patent applications, Serial Nos. 292,362, (filed August 28, 1939) and 297,955 (filed October 4, 1939) by Rothrock may be used. The butadiene polymers utilized in this invention are unlike the butadiene derivatives heretofore known. Previous attempts to polymerize butadiene and like substances have resulted in rubber or caoutchouc-like products. The products of this invention are uniform, viscous, and possess drying characteristics.

The polymers may be blown with air (or oxygen) before use, if desired. Such a treatment will decrease t e effective curing time of the polymeric material for anchorage purposes. Furthermore, they may be blown to a greater asvaeso w extent, without gelling, than products such as the well known drying oils. This enables them to be put, in a better condition for rapid coating composition application than the materials heretofore known. They may be applied without a drying catalyst, but such a procedure is not ordinarily employed because of the short drying times which are peculiar to the coating of cellulosic sheet.

The invention is not limited to cobalt and manganese naphthenates. Driers in general, for.

example, lead oleate, manganese rosinate, and the like, are quite satisfactory.

Although the moistureproofing coatings disclosed herein are especially applicable to sheets or films of regenerated cellulose (whether they be made by the viscose process, the cuprammonium process, or some other manufacturing technique), they may be used with varying degrees of desirableness on other bases. Sheets of cellulose ethers such as ethyl, benzyl, and glycol cellulose, cellulose esters such as cellulose nitrate and cellulose acetate, may be used.- The lowly esterified cellulosic compositions and low substituted cellulose ethers (U. S. A. Patent 2,123,883

. to Ellsworth) are especially suitable. Base films soluble in the solvent of the coating composition, are excluded. Other equivalent base materials are mentioned in the patents mentioned'herein;

Modifying ingredients for the anchoring coat a are described in the prior art patents, and in the interest of brevity a detailed description of the same is not given at this place. The poly.- mers may be applied without the use of a solvent or any modifying material, if desired.

As will be apparent from the specific examples,

"the composition of the surface moistureproofing coating mayvary widely' (being based, for example, upon cellulose derivatives, rubber derivatives, resins, etc.). The applicability of other suitable moistureproofing coating compositions 'will'be apparent to those skilled in the art.

3 A convenient test for anchorage is that utilized in the specific examples. It is carried out by immersing a strip of the coated, regenerated I cellulose in water at 25 C., and noting the time in hours necessary for the coating to be sufficiently loosened to allow removal of the coating by rubbing with the fingers.

Moistureproofness, moistureproofing and moistureproof materials and expressions are defined in U. S. A. Patent No. 2,147,180 (Ubben). In the interest of brevity the definitions are not repeated here. The terms and expressions re.- lated thereto and employed herein are used in accordance with such definitions.

The present invention has the advantages of the anchored moistureproof coating compositions of the prior art patents, and in addition has several important features not heretofore known. Unlike the previously employed synthetic and natural drying oils, the butadiene polymers of the present invention produce an odorless film. These butadiene polymers dry extremely rapidly,'which is not the case with drying oils. Drylngoils "dry relatively slowly, even in the presence of a drying catalyst.

The butadiene polymers cure to produce a nonv toxic film, thereby permitting an anchorage Process which is quite practical from a commercial viewpoint. In addition, when combined with In general, the coating compositions of the present invention, containing the diolefinic hydrocarbon polymers, are much harder and more wear-resistant than the previously known coating composition which contained drying oils. In addition, they set up and harden very much more rapidly than drying oils, and hence are much better suited for application by modern highspeed coating equipment.

As many apparently widely diflerent embodiments of this invention may be made' without departing from the spirit and scope thereof, it is to be understood that this invention is not limited to the specific embodiments thereof except- I as defined in the appended claims.

I claim:

1. In a method of moistureprooflng cellulosic sheet material. the steps of coating the sheet material with oily viscous butadiene polymeric ma"- terial, the said polymeric material being substantially identical with that obtained by polymerizing a member of the group consisting of butadiene and its open chain homologues under pressure at elevated temperatures in the presence of catalysts from the group consisting of sodium and salts of copper with weak acids in the presence of a carbonyl compound. to produce low condensed soluble polymer products, drying said coating and applying a moistureproofing coating composition on the first coating.

2. A moistureproof sheet wrapping material comprising a moistureproof coating anchored to a cellulosic base sheet with polymeric butadiene material, the said polymeric butadiene material being substantially identical with that obtained by polymerizing a member of the group consistingjof butadiene and its open chain homologues under pressure at elevated temperatures in the presence of catalysts from the group consisting oi sodium and salts of copper with weak acids in the presence of a carbonyl compound, to produce low condensed soluble polymer products.

of sodium and salts of copper with weak acids I in the presence of a carbonyl compound, to pro- ,duce low condensed soluble polymer products.

4. The process which comprises coating regenerated cellulose sheet with the butadiene drying polymer obtained by heating a mixture consisting of;

Parts Butadiene 3600 Benzene 780 n-Butyraldehyde 120,

, Catalyst (equal parts of copper acetate/H2O.

moistureproofing agents, they produce anchored coatings having better transparency, surface characteristics and moistureproofness than any such material previously known.

copper metal, iron powder, ferrous oxide)- 480 for 5 hours at C. with stirring, cooling, diluting with 6650 parts benzene, filtering off the catalyst, treating the filtrate with carbon black, and evaporating of! the benzene and by-product vinyl-cyclohexene; curing the. coating material to produce a non-tacky anchoring coating; and

6 thereafter top coating with a moistureproofing 5. The process which comprises coating regenerated cellulose sheet with the butadiene drying polymer obtained by heating a mixture consisting of i Parts Butadiene 3600 Benzene 780 n-Butyraldehyde 120 Catalyst (equal parts of copper acetate/H2O,

copper metal, iron powder, ferrous oxide)- 480 for 5 hours at 160 C. with stirring, cooling, diluting with 6650 parts benzene, filtering on the catalyst, treating the filtrate with carbon black, and evaporating oil the benzene and by-product vinyl-cyclohexene; curing the coating material to produce a non-tacky anchoring coat; and thereafter applying a moistureproofing coating comprising essentially nitrocellulose and paraflin wax.

6. The process which comprises coating regenerated cellulose sheet with the butadiene drying polymer obtained'by heating a mixture consisting of:

Parts Butadienei. 3600 Benz 780 n-Butyz'aldehyde 120 Catalyst (equal parts of copper acetate/H2O,

copper metal, iron powder, ferrous oxide) 480 for 5 hours at 160 C. with stirring, cooling, diluting with 6650 parts benzene, filtering ofi the catalyst, treating the filtrate with carbon black, and evaporating oil the benzene'and by-product vinyl-cyclohexene; curing the coating material to produce a non-tacky anchoring coat; and thereafter applying a moistureproofing coating.

7. The, process which comprises coating regenerated cellulose sheet with the butadiene drying polymer obtained by polymerizing a member of the group consisting of butadiene and its open chain homologues under pressure at elevated temperatures in'the presence of catalysts from the group consisting of sodium and salts of copper with weak acids in the presence of a carbonyl compound, to produce-low condensed soluble polymer products, curing the coating material to produce a non-tacky anchoring coat, and thereafter applying a moisture-proofing coating.

8. A moistureproof sheet wrapping material comprising a cellulosic base sheet having a moistureprooi' coating, the coating on the base sheet comprising essentially a moistureproofing coating and polymeric butadiene material obtainable by heating a mixture consisting of:

Parts Buta i 3600 Benzene 780 n-Butyraldehyde; 120

Catalyst (equal parts of copper acetate/H2O,

copper metal, iron powder, ferrous oxide) 480 for 5 hours at 160 C. with stirring, cooling, diluting with 6650 parts benzene, filtering oil the catalyst, treating the filtrate with carbon black, and

evaporating oil the benzene and by-product vinyl-cyclohexene.

9. A moistureproof sheet wrapping material comprising essentially a regenerated cellulose sheet having thereon a cured butadiene drying polymer coating; said butadiene drying polymer being obtainable by heating a mixture consisting of:

Parts Buta i n 3600 Benzene 780 n-Butyraldehyde Catalyst (equal parts of copper acetate/H2O,

copper metal, iron powder, ferrous oxide) 480 Parts Buta i 3600 Benzene 780 n-Butyraldehyde 120 Catalyst (equal parts of copper acetate/H2O,

copper metal, iron powder, ferrous oxide) 480 for 5 hours at C. with stirring, cooling, diluting with 6650 parts benzene, filtering oil the catalyst, treating the filtrate with carbon black,

and evaporating oil the benzene and by-product vinyl-cyclohexene, and superimposed on the butadiene drying polymer coating a moistureproofing coating consisting of:

. Parts Nitrocellulose (11.6% N) Parafiln wax (M. P. 60 C.) 3 Ester gum I 7 Dicyclohexyl phthalate 20 Dibutyl phthalate 10 JAMES A. MITCHELL. 

